WO2005097772A1 - Complexes de chromone - Google Patents

Complexes de chromone Download PDF

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Publication number
WO2005097772A1
WO2005097772A1 PCT/EP2005/002369 EP2005002369W WO2005097772A1 WO 2005097772 A1 WO2005097772 A1 WO 2005097772A1 EP 2005002369 W EP2005002369 W EP 2005002369W WO 2005097772 A1 WO2005097772 A1 WO 2005097772A1
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Prior art keywords
chain
formula
branched
preparation
straight
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PCT/EP2005/002369
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German (de)
English (en)
Inventor
Christophe Carola
Ralf Rosskopf
Herwig Buchholz
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Merck Patent Gmbh
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Priority to US10/594,752 priority Critical patent/US20070191305A1/en
Priority to EP05715783A priority patent/EP1732913A1/fr
Publication of WO2005097772A1 publication Critical patent/WO2005097772A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/738—Cyclodextrins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/007—Preparations for dry skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms

Definitions

  • the invention relates to complexes of certain chromone derivatives, preparations containing such derivatives, corresponding processes for the preparation of the chromone complexes or the preparations containing them and their use, in particular for the care, preservation or improvement of the general condition of the skin or hair.
  • the present invention also relates to cosmetic preparations for prophylaxis against suppuration processes in the skin.
  • Human skin is subject to certain aging processes, which are partly due to intrinsic processes (chronoaging) and partly to exogenous factors (environmental, e.g. photoaging).
  • temporary or permanent changes in the skin appearance can occur, such as acne, oily or dry skin, keratoses, rosaceae, photosensitive, inflammatory, erythematous, allergic or autoimmune-reactive reactions such as dermatoses and photodermatoses.
  • the exogenous factors include, in particular, sunlight or artificial radiation sources with a comparable spectrum, as well as compounds that can arise from the radiation, such as undefined reactive photo products, which can also be radical or ionic. These factors also include cigarette smoke and the reactive compounds contained therein, such as ozone, free radicals, for example the hydroxyl radical, singlet oxygen and other reactive oxygen or nitrogen compounds which disrupt the natural physiology or morphology of the skin.
  • MMPs matrix metalloproteinases
  • TIMPs tissue inhibitor of matrix metalloproteinases
  • the same factors also affect hair, where damage can also occur.
  • the hair becomes brittle, less elastic and lackluster.
  • the surface structure of the hair is damaged.
  • Cosmetic or dermatological care products with properties that counteract the described or comparable processes or that are intended to reduce or reverse the harmful effects are often characterized by the following specific properties - radical-catching, antioxidative, anti-inflammatory or moisturizing. Among other things, they prevent or reduce the activity of the matrix-degrading enzymes or regulate the new synthesis of collagen, elastin or proteoglycans.
  • antioxidants or radical scavengers in cosmetic preparations is known per se.
  • antioxidant vitamin E in sunscreen formulations is common. However, the effect achieved here still falls far short of the hoped-for effect.
  • Vitamin A and vitamin A derivatives act on the differentiation of epithelial cells and are therefore used for the prophylaxis and treatment of numerous phenomena affecting the skin condition; e.g. describes the use against acne, psoriasis, age spots, skin discoloration and wrinkles (see e.g. WO 93/19743, WO 02/02074).
  • R 1 and R 2 may be the same or different and are selected from
  • a first subject of the present invention are therefore complex compounds according to formula I.
  • R 3 represents H or straight-chain or branched d- to C 2 o -alkyl groups
  • R 4 stands for H or OR 8 ,
  • R 5 and R 6 may be the same or different and are selected from
  • Polyhydroxy compound such as preferably an ascorbic acid residue or glycosidic residues and
  • CD stands for a cyclodextrin molecule o stands for the number 1 and p stands for a number from the range 0.5 to 3.
  • a second subject of the present application are preparations containing a suitable carrier, characterized in that the preparations contain - 0.005 to 99% by weight of a complex compound according to formula I with residues as described above, or the preparation - 0.002 to 70% by weight % Cyclodextrin and - 0.001 to 60% by weight of at least one compound of the formula II or its topically tolerable salts and / or derivatives,
  • R 1 and R 2 may be the same or different and are selected from
  • R 3 represents H or straight-chain or branched Cr to C 2 o-alkyl groups
  • R 4 stands for H or OR 8 ,
  • R 5 and R 6 may be the same or different and are selected from
  • R 7 stands for H, straight-chain or branched Cr to C 2 o -alkyl groups, a polyhydroxy compound, such as preferably an ascorbic acid residue or glycosidic residues
  • the term “compound of the formula I or II” also includes the salts of the compounds of the formula I or II.
  • the preferred salts include in particular alkali metal and alkaline earth metal salts and ammonium salts, but in particular Sodium and potassium salts.
  • preparations according to the invention are usually either topically applicable preparations, for example cosmetic or dermatological formulations, or pharmaceuticals or foods or food supplements.
  • the preparations contain a cosmetic or dermatological or pharmaceutically or food-compatible carrier and, depending on the desired property profile, optionally further suitable ingredients.
  • Cyclodextrins are made up of 6, 7, 8 or even more ⁇ -1, 4-linked glucose units, the cyclohexaamylose (alpha- or ⁇ -cyclodextrin) differing in structure
  • Cycloheptaamylose (beta or ⁇ -cyclodextrin) is characterized by its structure
  • Cyclooctaamylose (gamma or ⁇ -cyclodextrin) is characterized by its structure
  • Cycloenneaamylose (delta- or ⁇ -cyclodextrin) is characterized by its structure
  • Chromon-cyclodextrin complexes are known in principle:
  • EP-A-0 424 444 discloses the use of salts of chromoncarboxylic acid in cosmetics to combat skin aging.
  • the compound shows a UV-filtering effect and has the following effects in animal experiments: the proportion of bound lipids in the skin increases, the proportion of soluble collagen in the skin increases, the resistance of the skin to the effects of the fibroplatic proteases collagenase and elastase elevated.
  • US Pat. No. 6,019,992 discloses cosmetic preparations which contain 4-chromanone and which are suitable for the treatment of aged, dry or wrinkled skin. It is shown that 4-chromanone in keratinocyte cultures promotes cell differentiation and stimulates lipid production.
  • EP-A-1 216 692 discloses the use of 2-methyl-2- ( ⁇ -carboxyethyl) chroman derivatives in cosmetic preparations. The preparations mentioned are particularly suitable for the prophylaxis against aging processes of skin and hair and for the prophylaxis against dry skin, wrinkling and pigment disorders.
  • the chromone derivatives e.g. Chromon, 7-hydroxychromon, 7-methoxychromone, 5,7-dihydroxy-2-methyl-chromon, 3-methyl -2-butenyloxy-chromon, 3-acetyl-5,7-dihydroxy-2-methyl-chromon, 5- hydroxychromone, n-pentyl-7-methoxychromone-2-carboxylate, n-undecyl-5-methoxychromone-2-carboxylate, 5-hydroxy-7-methoxy-2-methyl-chromone, 7-methoxy-chromon-2-carboxylic acid, n-Pentyl-chromon-2-carboxylic acid, 5-methoxychromone and chromon-2-carboxylic acid, are known from Japanese patent application JP 05/301813.
  • the chromone derivatives act as skin-compatible tyrosinase inhibitors, which reduce hyperpigmentation of the skin.
  • Japanese patent application JP 09/188608 describes the use of substituted chromone derivatives, such as, in particular, 5,7-dihydroxychromones, 7-methoxychromones, 5-hydroxy-7-methoxy-2-methylchromone and 5-hydroxy-2-methyl -chromon, known as an active ingredient against gray hair. The effect is attributed to the activation of the color pigment-forming cells and the increase in melanogenesis.
  • chromone derivatives which are substituted in position 2 with C ⁇ . ⁇ 5 alkyl and in position 7 have H, OH or alkoxy substitution, in combination with aminopropanol derivatives is known from JP 10/194919.
  • Cosmetic preparation the substituted chromone derivatives, such as 2- (l-ethylpentyl) chromone, 5,7-dihydroxychromones, 7-methoxychromones, 5-hydroxy-7-methoxy-2-methyl-chromone and 5-hydroxy-2 -Methyl-chrornon and aromatic compounds with a melting point of -10 ° C or above are known from JP 10/114640.
  • the chromone derivative makes it easier to incorporate the aromatic compound into the cosmetic formulation.
  • cyclodextrins ⁇ -cyclodextrins, preferably at one or more hydroxyl groups Ci. 24 alkyl or C ⁇ .
  • 2- Hydroxyalkyl-substituted gamma-cyclodextrins such as in particular hydroxypropyl- ⁇ -cyclodextrin, or mixtures of cyclodextrins, which contain at least 30% by weight, based on the total weight of the cyclodextrin mixture, of the above-mentioned ⁇ -cyclodextrins
  • the cyclodextrin content is 0.01-20.0% by weight, preferably 0.05-10.0% by weight, particularly preferably 0.1-5.0% by weight, based in each case on the Total weight of the composition is.
  • the proportion of the compounds of the formula II in the preparation 15 is preferably from 0.01 to 20% by weight, particularly preferably from 0.05 to 10% by weight and particularly preferably from 0.1 to 5% by weight, based on the entire preparation.
  • the proportion of the compounds of the formula II in the preparation is very particularly preferably from 0.1 to 2% by weight, based on the overall preparation.
  • Preferred uses according to the invention of the compounds of the formula I or of preparations comprising at least one compound according to formula I are in particular the use for prophylaxis against time and / or light-induced aging processes of human skin or human hair, in particular for prophylaxis against dry skin, wrinkling and / or pigment disorders, and / or for c. Reduction or prevention of damaging effects of UV rays on the skin, as well as prophylaxis against or reduction of skin imperfections, such as wrinkles, fine lines, rough skin or large-pored skin.
  • Formula I or preparations containing at least one compound according to formula I are further the use for the prophylaxis and / or prevention of premature skin aging, in particular for the prophylaxis and / or prevention of wrinkling of the skin due to light or aging, to reduce pigmentation and Keratosis actinica and for the prophylaxis and / or treatment of all diseases
  • Veruca plana Epidermodysplasia verruciformis, oral papillomatosis, Papillo-matosis florida, and the growths that can be caused by UV radiation, in particular the epithelioma basocellular and epithelioma spinocellulare.
  • preferred compounds of formula I also act as enzyme inhibitors. They presumably inhibit histidine decarboxyiase, protein kinases, elastase, aldose reductase and hyaluronidase, and therefore make it possible to maintain the integrity of the basic substance of vascular shells. Furthermore, they are believed to not specifically inhibit catechol-O-methyltransferase, increasing the amount of available catecholamines and thereby increasing vascular strength. They also inhibit AMP phosphodiesterase, which means that the substances have the potential to inhibit platelet aggregation.
  • the preparations according to the invention are generally suitable for immune protection and for protecting DNA and RNA.
  • the preparations are particularly suitable for protecting DNA and RNA against oxidative attacks, against radicals and against damage by radiation, in particular UV radiation.
  • Another advantage of the preparations according to the invention is cell protection, in particular the protection of Langerhans cells from damage caused by the above-mentioned influences. All of these uses or the use of the compounds of the formula I for the preparation of appropriately usable preparations are expressly the subject of the present invention.
  • the complex compounds or preparations containing the active ingredient combination according to the invention act synergistically in all these uses with respect to the individual components.
  • cyclodextrins and / or cyclodextrin derivatives to increase the solubility of is advantageous according to the invention
  • Compounds of the formula II Compounds of the formula II.
  • the use of cyclodextrins and / or cyclodextrin derivatives to improve the biological activity of compounds of the formula II is also advantageous.
  • chromene-4-one derivatives of the general formula I offers i.a. protection against damage caused directly or indirectly by UV radiation or processes caused by reactive compounds, e.g. B. skin aging, loss of skin moisture, loss of skin elasticity, the formation of wrinkles or wrinkles or pigment disorders or age spots.
  • the present invention relates to the use of the above. Preparations for the prevention of undesirable changes in the complexion, e.g. Acne or oily skin, keratosis, photosensitive, inflammatory, erythrematous, allergic or autoimmune reactive reactions.
  • undesirable changes in the complexion e.g. Acne or oily skin, keratosis, photosensitive, inflammatory, erythrematous, allergic or autoimmune reactive reactions.
  • the compounds or preparations according to the invention preferably also serve to soothe sensitive and irritated skin, for preventive regulation of the synthesis of collagen, hyaluronic acid, elastin, stimulation of DNA synthesis, in particular in the case of deficient or hypoactive skin conditions, regulation of transcription and translation of matrix-degrading enzymes , in particular the MMPs, increasing cell renewal and skin regeneration, increasing the skin's own protective and repair mechanisms for DNA, lipids and / or proteins.
  • R 3 stands for H and R 4 stands for OH since the active potential of representatives of this class of invention in the abovementioned sense is particularly high. If at least one of the radicals R 5 and R 6 additionally represents OH, these preferred compounds have, in addition to the properties mentioned above, an antioxidant potential. Therefore, they can act as an antioxidant in preparations.
  • Other compounds of formula I which are preferably used are characterized in that R 5 and R 6 are H. In this case, the residues R 3 and R 4 are freely accessible, which, as is assumed, is advantageous for the interaction with enzymes involved in the effects mentioned.
  • mono- or oligosaccharide residues can be used as glycoside residues.
  • Hexosyl radicals in particular ramnosyl radicals and glucosyi radicals, are preferred.
  • other hexosyl radicals for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be used advantageously. It may also be advantageous to use pentosyl residues.
  • the glycosyl radicals can be connected to the base body in an ⁇ - or ⁇ -glycosidic manner.
  • a preferred disaccharide is, for example, 6-0- (6-deoxy- ⁇ -L-mannopyranosyl) -ß-D-glucopyranoside.
  • the chromone portion of the compound I is preferably a compound selected from the compounds having the formulas IIIa-IIn:
  • chromone components of the compounds of the formula I or compounds of the formula II can be prepared by methods which are well known to the person skilled in the art and are described in the literature (for example in standard works such as Houben-Weyl, methods of organic chemistry, Georg-Thieme Verlag, Stuttgart), won or manufactured.
  • 5,7-dihydroxy-2-methyl-chromen-4-one occurs in plants and can be obtained by extraction.
  • the plant extracts are produced by customary methods of extracting the plants or parts of plants. Suitable extraction methods can be: Maceration, remaceration, digestion, movement maceration, vortex extraction, ultrasound extraction, counter-current extraction, percolation, repercolation, evacolation, diacolation or solid-liquid extraction with continuous reflux, which is carried out in a Soxhlet extractor.
  • Water or an alcohol, for example, can be used as the solvent for the extraction.
  • the last step, the selective saponification of the 7 acetyl groups in compound 7, can be carried out according to the method described in G. Zemplen, Chem. Ber. 59 (1926) 1258. This is done using a catalytic amount of NaOCH 3 and a calculated amount of methanol.
  • the esterification of glycosidic OH groups with aromatic sulfonic acid units can be carried out, for example, according to the method described in A.B. Foster et al., J. Chem. Soc. (1954) 3625-3629. Thereafter the sugar component can e.g. be reacted with an appropriate aromatic sulfonic acid chloride in pyridine.
  • the etherification of glycosidic OH groups with aromatic residues can be carried out, for example, according to the method described in P. Beraud et al., Tetrahedron Let. 30 (3) (1989) 325-326. In this Mitsunobu reaction, the etherification takes place, for example, in such a way that the sugar component is dissolved together with triphenylphosphine PPh 3 in pyridine and reacted with a corresponding phenol component and diethyl azodicarboxylate.
  • the etherification of glycosidic OH groups with residues of saturated hydrocarbons can take place, for example, according to the method described in M. Goebel et al., Tetrahedron 53 (9) (1997) 3123-3134.
  • the etherification takes place e.g. such that the sugar component is carefully mixed with sodium hydride in dry dimethylformamide under inert gas and then with a suitable alkylating reagent such as e.g. an appropriate bromide is carefully implemented.
  • the complex compounds of formula I can be prepared, preferably by compounds of formula II with cyclodextrins in solution at elevated temperature.
  • a corresponding method is a further subject of the present invention.
  • Corresponding compounds can be prepared if the cyclodextrin is used in excess or exactly in a molar ratio of 2: 1 based on the chromone.
  • the preparation is a preparation for protecting body cells against oxidative stress, in particular for reducing skin aging, characterized in that, in addition to the one or more compounds of the formula I or the formula II or contains several other antioxidants.
  • antioxidants there are many proven substances known from the specialist literature that can be used as antioxidants, e.g. Amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole (e.g. urocanic acid) and their derivatives, peptides such as D, L-camosine, D-carnosine, L-camosine and their derivatives (e.g. anserine), carotenoids,
  • Amino acids e.g. glycine, histidine, tyrosine, tryptophan
  • imidazole e.g. urocanic acid
  • peptides such as D, L-camosine, D-carnosine, L-camosine and their derivatives (e.g. anserine), carotenoids,
  • Carotenes e.g. ⁇ -carotene, ß-carotene, lycopene
  • chlorogenic acid and their derivatives e.g. dihydroliponic acid
  • aurothioglucose e.g. aurothioglucose
  • propylthiouracil e.g.
  • thioredoxin glutathione, cysteine, cystine, Cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their
  • salts dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthioninsulfoximines, Homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerable doses (e.g. pmol to ⁇ mol / kg), also (metal) chelators (e.g.
  • ⁇ -hydroxy fatty acids palmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g. citric acid, c lactic acid, malic acid
  • humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives
  • vitamin C and derivatives e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, Ascorbyl acetate
  • tocopherols and derivatives e.g. vitamin E acetate
  • vitamin A and derivatives e.g. vitamin A palmitate
  • mixtures are, for example, mixtures containing lecithin, L - (+) - ascorbyl palmitate and citric acid (for example (eg Oxynex ® AP), natural tocopherols, L - (+) - ascorbyIpalmitate, L - (+) -
  • antioxidants are usually used with compounds of the formula I or formula II in such compositions in ratios in the range from 1000: 1 to 1: 1000, preferably in amounts from 100: 1 to 1: 100.
  • the preparations according to the invention can contain 30 vitamins as further ingredients.
  • Vitamins and vitamin derivatives are preferably selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamine chloride hydrochloride (vitamin Bi), Riboflavin (Vitamin B 2 ), Nicotinamide, Vitamin C (Ascorbic Acid), Vitamin D, Ergocalciferol (Vitamin D), Vitamin E, DL- ⁇ -Tocopherol, Tocopherol-E-Acetate, Tocopherol Hydrogen Succinate, Vitamin K- ⁇ , Esculin (Vitamin P -Wirkstoff), thiamine (vitamin Bi), nicotinic acid (niacin) pyri t e Doxin, pyridoxal, pyridoxamine (vitamin B6), pantothenic acid, biotin, folic acid and cobalamin (vitamin B present in the inventive cosmetic preparations 12) , particularly preferably vitamin
  • the polyphenols are particularly interesting for applications in the pharmaceutical, cosmetic or nutritional field.
  • the flavonoids or bioflavonoids which are mainly known as plant dyes, often have an antioxidant potential.
  • K. Lemanska, H. Szymusiak, B. Tyrakowska, R. Zielinski, IMCM Rietjens deal with effects of the substitution pattern of mono- and dihydoxyflavones; Current Topics in Biophysics 2000, 24 (2), 101-108.
  • Preparations which are particularly preferred according to the invention contain, in addition to the compounds of the formula I or formula II, UV filters.
  • the UV-sensitive dibenzoylmethane derivatives are additionally stabilized by the presence of the compounds of the formula I or formula II .
  • Another object of the present invention is therefore the use of the compounds of the formula I or formula II for stabilizing dibenzoylmethane derivatives in preparations.
  • UV filters can be used in combination with the compounds of the formula I or formula II according to the invention.
  • Those UV filters whose physiological harmlessness has already been proven are particularly preferred.
  • Both for UVA and UVB filters there are many well-known and proven substances from the specialist literature, e.g.
  • Benzylidene camphor derivatives such as 3- (4'-methylbenzylidene) dl camphor (e.g. Eusolex® 6300), 3-benzylidene camphor (e.g. Mexoryl® SD), polymers of
  • Benzoyl- or dibenzoylmethanes such as 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione (e.g. Eusolex® 9020) or 4-isopropyldibenzoylmethane (e.g. Eusolex® 8020),
  • Benzophenones such as 2-hydroxy-4-methoxybenzophenone (e.g. Eusolex® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (e.g. Uvinul® MS-40),
  • Methoxycinnamic acid esters such as octyl methoxycinnamate (e.g. Eusolex® 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of the isomers (e.g. Neo Heliopan® E 1000),
  • Salicylate derivatives such as 2-ethylhexyl salicylate (e.g. Eusolex® OS), 4-isopropylbenzyl salicylate (e.g. Megasol®) or 3,3,5-
  • Trimethylcyclohexyl salicylate e.g. Eusolex® HMS
  • 4-aminobenzoic acid and derivatives such as 4-aminobenzoic acid, 4- (dimethylamino) benzoic acid-2-ethylhexyl ester (e.g. Eusolex® 6007), ethoxylated 4-aminobenzoic acid ethyl ester (e.g. Uvinul® P25),
  • Phenylbenzimidazole sulfonic acids such as 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts (e.g. Eusolex® 232), 2,2- (1,4-phenylene) bisbenzimidazole-4,6-disulfonic acid or their salts ( eg Neoheliopan® AP) or 2,2- (1,4-phenylene) bisbenzimidazole-6-sulfonic acid;
  • organic UV filters are generally incorporated into cosmetic formulations in an amount of 0.5 to 10 percent by weight, preferably 1-8%.
  • UV filters are also methoxy flavones according to the older German patent application DE-A-10232595.
  • Organic UV filters are generally incorporated into cosmetic formulations in an amount of 0.5 to 20 percent by weight, preferably 1-15%.
  • Inorganic UV filters include those from the group of titanium dioxides such as coated titanium dioxide (e.g. Eusolex® T-2000, Eusolex ® T-AQUA, Eusolex® T-AVO), zinc oxides (e.g. Sachtotec®), iron oxides or cerium oxides , These inorganic UV filters are generally incorporated into cosmetic preparations in an amount of 0.5 to 20 percent by weight, preferably 2 to 10%.
  • Preferred compounds with UV-filtering properties are 3- (4 ' - methylbenzylidene) -dl-camphor, 1- (4-tert-butylphenyl) -3- (4-methoxy-phenyl) - pro-pan-1, 3- dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl methoxycinnamate, 3,3,5-trimethylcyclohexyl salicylate, 4- (dimethyiamino) 2-ethylhexyl benzoate, 2-cyano -3,3-
  • the protective effect against harmful effects of UV radiation can be optimized by combining one or more compounds of the formula I or formula II with further UV filters.
  • Optimized compositions can, for example, combine the organic UV filters 4'-methoxy-6-hydroxyflavon with 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione and 3- (4 ' - Methylbenzylidene) -dl-camphor contain. This combination gives p p . a broadband protection that can be supplemented by adding inorganic UV filters such as titanium dioxide microparticles.
  • UV filters mentioned can also be used in encapsulated form.
  • the individual advantages are as follows: -
  • the hydrophilicity of the capsule wall can be set independently of the solubility of the UV filter.
  • you can Hydrophobic UV filters can be incorporated into purely aqueous preparations.
  • the oily impression which is often perceived as unpleasant, is prevented when the preparation containing the hydrophobic UV filter is applied.
  • Certain UV filters, especially dibenzoylmethane derivatives show only a reduced photostability in cosmetic preparations. By encapsulating these filters or compounds that impair the photostability of these filters, such as cinnamic acid derivatives, the photostability of the entire preparation can be increased.
  • UV filters are in encapsulated form. It is advantageous if the capsules are so small that they cannot be observed with the naked eye. To achieve the above Effects, it is also necessary that the capsules are sufficiently stable and do not release the encapsulated active ingredient (UV filter) into the environment or only to a small extent.
  • Suitable capsules can have walls made of inorganic or organic polymers.
  • US 6,242,099 B1 describes the production of suitable capsules with walls made of chitin, chitin derivatives or polyhydroxylated polyamines.
  • Capsules to be used particularly preferably according to the invention have walls which can be obtained by a SolGel process, as described in the applications WO 00/09652, WO 00/72806 and WO 00/71084.
  • Capsules, the walls of which are made of silica gel (silica; undefined silicon oxide hydroxide) are constructed.
  • the production of corresponding capsules is known to the person skilled in the art, for example from the cited patent applications, the content of which expressly belongs to the subject of the present application.
  • the capsules in preparations according to the invention are preferably contained in amounts which ensure that the encapsulated UV filters in the amounts specified above in the
  • the preparations according to the invention can also contain other customary skin-protecting or skin-care active ingredients. In principle, these can be all active ingredients known to the person skilled in the art.
  • the preparation according to the invention contains at least one repellent, the repellent preferably being selected from N, N-diethyl-3-methylbenzamide, 3- (acetyl-butylamino) propionic acid, ethyl ester, dimethyl phthalate, butopyronoxyl, 2, 3,4,5-bis- (2-butylene) -tetrahydro-2-furaldehyde, N, N-caprylic acid diethylamide, N, N-diethylbenzamide, o-chloro-N, N-diethylbenzamide, dimethylcarbate, di-n-propylisocinchomeronate, 2-ethylhexane-1,3-diol, N-octyl-bicyclohepetene diecarboximide, piperonyl butoxide, 1- (2-
  • Methylpropyloxycarbonyl) -2- (hydroxyethyl) piperidine or mixtures thereof it being particularly preferably selected from N, N-diethyl-3-methylbenzamide, ethyl 3- (acetyl-butylamino) propionate 1- (2-methylpropyloxycarbonyl) ) -2- (hydroxyethyl) piperidine or mixtures thereof.
  • the preparations according to the invention which contain repellents are preferably insect repellants.
  • Insect repellents are offered in the form of solutions, gels, pens, rollers, pump sprays and aerosol sprays, with solutions and sprays forming the main part of the commercially available products.
  • the basis for these two product forms are mostly alcoholic or aqueous-alcoholic solutions with the addition of fatty substances and light perfuming.
  • compatible solutes are substances that are involved in the osmoregulation of plants or microorganisms and can be isolated from these organisms.
  • the generic term compatible solutes also includes the osmolytes described in German patent application DE-A-10133202. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids and their precursors. In the sense of German patent application DE-A-10133202, osmolytes are understood in particular to be substances from the group of polyols, such as, for example, myo-inositol, mannitol or sorbitol and / or one or more of the osmolytically active substances mentioned below:
  • Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine, phosphatidylinositol, inorganic phosphates, proteins, peptides and polyamic acids.
  • Precursors are e.g. B. Compounds that are converted to osmolytes by metabolic steps.
  • compatible solutes are preferably selected from the group consisting of pyrimidinecarboxylic acids (such as ectoin and hydroxyectoin), proline, betaine, glutamine, cyclic diphosphoglycerate, N.-acetylomithine, trimethylamine-N-oxide di-myo-inositol-phosphate (DIP) , cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), ß-mannosylglycerate (Firoin), ß-mannosylglyceramide (Firoin-A) and / or di-mannosyl-di-inositol phosphate (DMIP) or an optical isomer, derivative, for example an acid, a salt or ester of these compounds or combinations thereof.
  • pyrimidinecarboxylic acids such as ectoin and hydroxyectoin
  • proline such as ectoin and
  • pyrimidinecarboxylic acids are especially ectoin ((S) - 1, 4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoin ((S, S) -1, 4,5,6-tetrahydro-5 -hydroxy-2-methyl-4-pyrimidinecarboxylic acid and its derivatives, which stabilize enzymes and other biomolecules in aqueous and organic solutions
  • Solvents Furthermore, they particularly stabilize enzymes against denaturing conditions, such as salts, extreme pH values, surfactants, urea, guanidinium chloride and other compounds.
  • Ectoin and ectoin derivatives such as hydroxyectoin can advantageously be used in drugs.
  • hydroxyectoin can be used to produce a medicament for the treatment of skin diseases.
  • Other areas of application of the hydroxyectoin and other ectoin derivatives are typically in areas in which e.g. Trehalose is used as an additive.
  • Ectoin derivatives such as hydroxyectoin can be used as a protective substance in dried yeast and bacterial cells.
  • pharmaceutical products such as non-glycosylated, pharmaceutically active peptides and proteins e.g. t-PA can be protected with ectoin or its derivatives.
  • Cosmetic applications include in particular the use of ectoin and ectoin derivatives for the care of aged, dry or irritated skin.
  • European patent application EP-A-0 671 161 describes in particular that ectoin and hydroxy-ectoin are used in cosmetic preparations such as powders, soaps, surfactant-containing cleaning products, lipsticks, blushes, make-ups, skin care creams and sunscreen preparations.
  • a pyrimidine carboxylic acid according to formula IV below is preferably used,
  • R 1 is H or C1-8-alkyl
  • R 2 is H or C1-4-alkyl
  • R 3 , R 4 , R 5 and R 6 are each independently a group from the group H, OH, NH 2 and are C1-4 alkyl.
  • Pyrimidinecarboxylic acids in which R 2 is a methyl or an ethyl group and R 1 or R 5 and R 6 are H are preferably used.
  • the preparations according to the invention preferably contain pyrimidinecarboxylic acids of this type in amounts of up to 15% by weight.
  • the pyrimidinecarboxylic acids are preferably used in ratios of 100: 1 to 1: 100 to the compounds of the formula I, ratios in the range 1:10 to 10: 1 being particularly preferred.
  • the compatible solutes are selected from di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1,1-diglycerol phosphate (DGP), ⁇ -mannosylglycerate ( Firoin), ⁇ -mannosylglyceramide (Firoin-A) and / or dimannosyl-di-inositol phosphate (DMIP), ectoin, hydroxyectoin or mixtures thereof.
  • DIP di-myo-inositol phosphate
  • cDPG cyclic 2,3-diphosphoglycerate
  • DGP 1,1-diglycerol phosphate
  • Firoin ⁇ -mannosylglycerate
  • Firoin-A ⁇ -mannosylglyceramide
  • DMIP dimannosyl-di-inositol phosphate
  • 2-hydroxy-5-methyllaurophenone oxime which is also referred to as HMLO, LPO or F5
  • HMLO 2-hydroxy-5-methyllaurophenone oxime
  • LPO 2-hydroxy-5-methyllaurophenone oxime
  • Preparations which contain 2-hydroxy-5-methyllaurophenonoxime are therefore suitable for the treatment of skin diseases which are associated with inflammation. It is known, that such preparations can be used, for example, for the therapy of psioriasis, various forms of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the appendages of the skin.
  • Preparations according to the invention which, in addition to the compound of the formula I, additionally contain an aryl oxime, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising anti-inflammatory suitability.
  • the preparations preferably contain 0.01 to 10% by weight of the aryloxime, it being particularly preferred if the preparation contains 0.05 to 5% by weight aryloxime.
  • the preparation according to the invention contains at least one self-brewing agent.
  • H 2 C-OH H 2 C-OH HC 0 H 2 C-OH erolaldehyc 1 hydroxymethylglyoxal ⁇ -dialdehyde erythrulose
  • 6-Aldo-D-fructose ninhydrin Also worth mentioning is 5-hydroxy-1,4-naphthoquinone (juglone), which is extracted from the shells of fresh walnuts
  • 1,3-Dihydroxyacetone (DHA), a trivalent sugar occurring in the human body and its derivatives, is very particularly preferred.
  • the preparations according to the invention can also contain dyes and color pigments.
  • the dyes and pigments can be selected from the corresponding positive list in the Cosmetics Regulation or the EC list of cosmetic colorants. In most cases, they are identical to the colorants approved for food.
  • Advantageous color pigments are, for example, titanium dioxide, mica, Iron oxides (e.g. Fe 2 0 3 , Fe 3 0, FeO (OH)) and / or tin oxide.
  • Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramerine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the list below.
  • the Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society of Dyers and Coiourists, Bradford, England, 1971.
  • oil-soluble natural dyes such as. B. paprika extract, ß-carotene or cochineal.
  • Gel creams containing pearlescent pigments are also advantageous for the purposes of the present invention.
  • the types of pearlescent pigments listed below are particularly preferred: 1. Natural pearlescent pigments, such as. B. 1. "fish silver” (guanine / hypoxanthine mixed crystals from fish scales) and 2. “mother-of-pearl” (milled mussel shells) 2. monocrystalline pearlescent pigments such as B. bismuth oxychloride (BiOCI) 3rd layer substrate pigments: e.g. B. mica / metal oxide
  • Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Z is particularly advantageous.
  • pearlescent pigment types based on mica / metal oxide are also advantageous:
  • B the pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona.
  • Timiron Timiron
  • Colorona Colorona
  • Dichrona The list of the pearlescent pigments mentioned is of course not intended to be limiting.
  • Pearlescent pigments which are advantageous in the sense of the present invention can be obtained in numerous ways known per se. For example, other substrates can also be used
  • Coating mica with other metal oxides such as. B. silica and the like. Z are advantageous.
  • Pearlescent pigments which are produced using SiO 2 are particularly preferred. Such pigments, which can also have gonichromatic effects, are e.g. B. available under the trade name Sicopearl Fantastico from BASF.
  • Pigments from Engelhard / Mearl can also be advantageous
  • effect pigments which are available from Flora Tech under the trade name Metasomes Standard / Glitter in various colors (yellow, red, green, blue).
  • the glitter particles are present in mixtures with various auxiliaries and dyes (such as the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).
  • the dyes and pigments can be present either individually or in a mixture and can be coated with one another, different color effects generally being produced by different coating thicknesses.
  • the total amount of dyes and coloring pigments is advantageously from the range of z. B. 0.1% by weight to 30% by weight, preferably from 0.5 to 15% by weight, in particular from 1.0 to 10% by weight, in each case based on the total weight of the preparations.
  • the one or more compounds of the formula I can be incorporated into cosmetic or dermatological preparations in the customary manner. Preparations are suitable for external use, for example as a cream, lotion, gel, or as a solution which can be sprayed onto the skin. Dosage formulas such as capsules, coated tablets, powders, tablet solutions or solutions are suitable for internal use.
  • preparations according to the invention e.g. called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays.
  • Other forms of application are e.g. Sticks, shampoos and shower baths. Any customary carriers, auxiliaries and, if appropriate, further active ingredients can be added to the preparation.
  • Preferred auxiliaries come from the group of preservatives, antioxidants, stabilizers, solubilizers, vitamins, colorants, odor improvers.
  • Ointments, pastes, creams and gels can contain the usual carriers, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.
  • carriers e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.
  • Powders and sprays can contain the usual carriers, eg milk sugar, talc, silica, aluminum hydroxide, calcium silicate and Polyamide powder or mixtures of these substances.
  • Sprays can also contain the usual blowing agents, eg chlorofluorocarbons, propane / butane or dimethyl ether.
  • Solutions and emulsions can contain the usual carriers such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerol fatty acid esters, polyethylene glycols and fatty acid esters of sorbitol contain these substances.
  • solvents e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butyl glycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerol fatty acid
  • Suspensions can be the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar agar and tragacanth or mixtures of these substances.
  • liquid diluents e.g. Water, ethanol or propylene glycol
  • suspending agents e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar agar and tragacanth or mixtures of these substances.
  • Soaps can contain the usual carriers such as alkali salts of fatty acids, salts of fatty acid half-esters, fatty acid protein hydrolyzates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugar or mixtures of these substances.
  • Surfactant-containing cleansing products may comprise the customary carriers, such as salts of fatty alcohol sulfates, Sulfobemstein- acid monoesters, fatty acid protein hydrolysates, isethionates, imidazolinium derivatives, betaines methyl taurates, sarcosinates, Fettchureamidethersulfate, alkyl, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol - contain fatty acid esters or mixtures of these substances.
  • customary carriers such as salts of fatty alcohol sulfates, Sulfobemstein- acid monoesters, fatty acid protein hydrolysates, isethionates, imidazolinium derivatives, betaines methyl taurates, sarcosinates, Fettklareamidethersulfate, alkyl, fatty alcohols, fatty acid glycer
  • Face and body oils can contain the usual carriers such as synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily plant extracts, paraffin oils, lanolin oils or mixtures of these substances.
  • synthetic oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily plant extracts, paraffin oils, lanolin oils or mixtures of these substances.
  • Other typical cosmetic application forms are also lipsticks, lip care sticks, mascara, eyeliner, eye shadows, blush, powder, emulsion and wax make-up as well as sun protection, pre-sun and after-sun preparations.
  • the preferred preparation forms according to the invention include in particular emulsions.
  • Emulsions according to the invention are advantageous and contain z.
  • Oils such as triglycerides of capric or caprylic acid, further natural oils such as B. castor oil;
  • Fats, waxes and other natural and synthetic fat bodies preferably esters of fatty acids with alcohols of low C number, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids; - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.
  • the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms.
  • ester oils can then advantageously be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of
  • the oil phase can advantageously be chosen from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12-18, carbon atoms.
  • the fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, e.g. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
  • any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
  • the oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, Ci 2 -i 5 -alkyl benzoate, caprylic-capric acid triglyceride, dicapryl ether.
  • hydrocarbons paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.
  • the oil phase can also advantageously have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.
  • Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention.
  • other silicone oils can also be used advantageously for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
  • the aqueous phase of the preparations according to the invention advantageously advantageously contains alcohols, diols or polyols of low C number, and also their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene - Glycol monomethyl or monoethyl ether and similar products, furthermore alcohols of low C number, e.g.
  • isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners which or which can advantageously be selected from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for example Hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • Water can also be a component of alcoholic solvents.
  • Emulsions according to the invention are advantageous and contain z.
  • the preparations according to the invention contain hydrophilic surfactants.
  • hydrophilic surfactants are preferably selected from the group of alkyl glucosides, acyl lactylates, betaines and cocoamphoacetate.
  • alkyl glucosides are in turn advantageously selected from the group of alkyl glucosides, which are characterized by the structural formula
  • R is a branched or unbranched alkyl radical having 4 to 24 carbon atoms and where DP is an average degree of glucosylation of up to 2.
  • P- ⁇ , p 2 , P3 ⁇ •• or pi represent the proportion of single, double, triple ... i-fold glucosylated products in percentages by weight.
  • products with degrees of glucosylation of 1-2 are particularly advantageous from 1, 1 to 1, 5, very particularly advantageously selected from 1, 2-1, 4, in particular from 1, 3.
  • the value DP takes account of the fact that alkylglucosides are generally mixtures of mono- and oligoglucosides due to their production.
  • Alkylglylcosides which are used particularly advantageously according to the invention are selected from the group consisting of octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, undecylglucopyranoside, dodecylglucopyranoside, tetrahedronylglucopyranoside and hexadecylglucopyranoside.
  • R 1 is a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M + is selected from the group of alkali ions and the group of ammonium ions substituted with one or more alkyl and / or with one or more hydroxyalkyl radicals or corresponds to half the equivalent of an alkaline earth ion.
  • R 2 is a branched or undisclosed alkyl radical having 1 to 30 carbon atoms.
  • R 2 particularly advantageously denotes a branched or unbranched alkyl radical having 6 to 12 carbon atoms.
  • Capramidopropylbetaine for example the product Tego ® Betaine is advantageous, for example 810 from Th. Goldschmidt AG.
  • the cocoamphoacetate which is advantageous according to the invention is, for example, sodium cocoamphoacetate, as is known by the company Miranol Chemical Corp. under the name Miranol G Ultra C32. is available.
  • the preparations according to the invention are advantageously characterized in that the hydrophilic surfactant or surfactants in concentrations of 0.01-20% by weight, preferably 0.05-10% by weight, particularly preferably 0.1-5% by weight, in each case based on the total weight of the composition, is or are present.
  • the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • Cosmetic and dermatological preparations according to the invention can be in various forms. So you can z. B. a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) or oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type Oil-in-water (W / O / W), a gel, a solid stick, an ointment or an aerosol. It is also advantageous to give ectoine in an encapsulated form, e.g. B. in collagen matrices and other common encapsulation materials, e.g. B.
  • Emulsions are preferred. O / W emulsines are particularly preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.
  • the known W / O and O / W emulsifiers can be used as emulsifiers. It is advantageous to use other customary co-emulsifiers in the preferred O / W emulsions according to the invention.
  • O / W emulsifiers are advantageously chosen as co-emulsifiers, primarily from the group of substances with HLB values of 11-16, very particularly advantageously with HLB values of 14.5-15.5, provided that the O / W emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value of such emulsifiers can also be lower or higher.
  • fatty alcohol ethoxylates from the group of ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).
  • Particularly preferred are: polyethylene glycol (13) stearyl ether (steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (steareth-16), Polyethylene glycol (17) - stearyl ether (Steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (Steareth-19), polyethylene glycol (20) - stearyl ether (Steareth-20), polyethylene glycol (12) isostearyl ether (isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), polyethylene glycol (14)
  • Sodium laureth-11 carboxylate can advantageously be used as the ethoxylated alkyl ether carboxylic acid or its salt.
  • Sodium laureth-4 sulfate can advantageously be used as the alkyl ether sulfate.
  • Polyethylene glycol (30) cholesteryl ether can advantageously be used as the ethoxylated cholesterol derivative.
  • Polyethylene glycol (25) soyasterol has also proven itself.
  • polyethylene glycol glycerol fatty acid esters from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / cprinate, polyglycol
  • sorbitan esters from the group consisting of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate,
  • W / O emulsifiers can be used:
  • W / O emulsifiers are glyceryl monostearate, glyceryl, glyceryl monomyristate, glyceryl monostearate, diglyceryl monostearate, Diglycerylmonoisostearat, propylene glycol, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol, sorbitan, sorbitan, sorbitan, Sorbitanmonoisooleat, sucrose, cetyl alcohol, stearyl alcohol, arachidyl, behenyl, Isobehenyl alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (Steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl monocaprylate.
  • Preparations preferred according to the invention are particularly suitable for protecting human skin against aging processes and against oxidative processes
  • Sun radiation, heat or other influences are generated. there it is available in various dosage forms commonly used for this application. It can be used in particular as a lotion or emulsion, such as a cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, as solid pins or as
  • a lotion or emulsion such as a cream or milk (O / W, W / O, O / W / O, W / O / W)
  • oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions as solid pins or as
  • the preparation may contain cosmetic adjuvants which are commonly used in this type of preparation, e.g. Thickeners, softeners, wetting agents, surfactants, emulsifiers, preservatives, anti-foaming agents, perfumes, waxes, lanolin, blowing agents, dyes and / or pigments which color the agent itself or the skin, and others commonly used in cosmetics ingredients.
  • cosmetic adjuvants which are commonly used in this type of preparation, e.g. Thickeners, softeners, wetting agents, surfactants, emulsifiers, preservatives, anti-foaming agents, perfumes, waxes, lanolin, blowing agents, dyes and / or pigments which color the agent itself or the skin, and others commonly used in cosmetics ingredients.
  • An oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof can be used as the dispersing or solubilizing agent.
  • the particularly preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerin and sorbitol.
  • a preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and, in addition to the compound or compounds of the formula I or formula II, for example fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and Contains emulsifiers in the presence of water.
  • fatty alcohols for example fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and Contains emulsifiers in the presence of water.
  • the preparation according to the invention can also be in the form of an alcoholic gel which comprises one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerol, and a thickener, such as silica.
  • the oily-alcoholic gels also contain natural or synthetic oil or wax.
  • the solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.
  • a preparation is packaged as an aerosol, the usual propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes, are generally used.
  • the cosmetic preparation can also be used to protect the hair against photochemical damage, to prevent changes in color shades, discoloration or damage of a mechanical nature.
  • it is suitably packaged as a shampoo, lotion, gel or emulsion for rinsing, the respective preparation being applied before or after shampooing, before or after dyeing or decoloring or before or after the perm.
  • a preparation can also be selected as a lotion or gel for styling and treatment, as a lotion or gel for brushing or laying a water wave, as a hair lacquer, permanent wave agent, dye or bleaching agent for the hair.
  • the preparation with light protection properties can contain various adjuvants used in this type of agent, such as interfaces, active agents, thickeners, polymers, plasticizers, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils , Waxes, anti-greasing agents, dyes and / or pigments that color the agent itself or the hair or other ingredients commonly used for hair care.
  • adjuvants used in this type of agent such as interfaces, active agents, thickeners, polymers, plasticizers, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils , Waxes, anti-greasing agents, dyes and / or pigments that color the agent itself or the hair or other ingredients commonly used for hair care.
  • Further objects of the present invention are a method for producing a preparation, which is characterized in that at least one compound of formula I or formula II with residues such as described above is mixed with a cosmetically or dermatologically or food-compatible carrier, and the use of a compound of formula I or formula II for the preparation of a preparation.
  • compositions according to the invention can be prepared using
  • the mixing can result in dissolving, emulsifying or dispersing the compound of the formula I or formula II in the carrier.
  • compounds of the formula I or formula II can have a stabilizing effect on the preparation. When used in corresponding products, they therefore remain stable for longer and do not change their appearance. In particular, even with prolonged use or longer storage, the effectiveness of the ingredients, e.g. Vitamins. Among other things, this is particularly advantageous in the case of compositions for protecting the skin against the action of UV rays, since these cosmetics are exposed to particularly high levels of exposure to UV radiation.
  • the foodstuffs which can be enriched with one or more compounds of the formula I or formula II according to the present invention comprise all materials which are suitable for consumption by animals or are suitable for human consumption, for example vitamins and provitamins thereof, "fats, minerals or amino acids".
  • the foods can be solid but also liquid, that is to say they can be present as a drink).
  • the present invention further relates to the use of a compound of the formula I or formula II as a food additive for human or animal nutrition and preparations which are food or food supplements and contain appropriate carriers.
  • Foods which can be enriched with one or more compounds of the formula I or formula II according to the present invention are, for example, foods which come from a single natural source, such as e.g. Sugar, unsweetened juice, nectar or puree from a single plant species, e.g. unsweetened apple juice (for example also a mixture of different types of apple juice), grapefruit juice, orange juice, apple compote, apricot nectar, tomato juice, tomato sauce, tomato puree etc.
  • Further examples of foods enriched according to the present invention with one or more compounds of the formula I or formula II are grain of a single plant species and materials made from such plant species, such as Cereal syrup, rye flour, wheat flour or oat bran.
  • Mixtures of such foods are also suitable for being enriched according to the present invention with one or more compounds of the formula I or formula II, for example multi-vitamin preparations, mineral mixtures or sugared juice.
  • Further examples of foods which can be enriched with one or more compounds of the formula I or formula II according to the present invention are food preparations, for example prepared cereals, pastries, mixed drinks, foods specially prepared for children, such as yogurt, diet foods, low-calorie Food or animal feed called.
  • the foods which are enriched according to the present invention with one or more compounds of the formula I or formula II can thus include all edible combinations of carbohydrates, lipids, proteins, inorganic elements, trace elements, vitamins, water or active metabolites of plants and animals.
  • the foods which can be enriched with one or more compounds of formula I or formula II according to the present invention are preferably administered orally, e.g. in the form of dishes,
  • the foods according to the invention enriched with one or more compounds of the formula I or formula II can be prepared using techniques which are well known to the person skilled in the art.
  • compounds of the formula I have only a weakly pronounced inherent color.
  • the weakly pronounced inherent color is e.g. This is of great advantage if the ingredients' own color of the ingredients is undesirable for aesthetic reasons.
  • the proportion of the compounds of the formula I in the preparation is preferably from 0.01 to 20% by weight, particularly preferably from 0.05 to 10% by weight and particularly preferably from 0.1 to 5% by weight, based on the overall preparation ,
  • the proportion of the compounds of the formula I in the preparation is very particularly preferably from 0.1 to 2% by weight, based on the preparation as a whole.
  • the ester is obtained by transesterification of the acid from Example 2 with 1-ethylhexyl alcohol.
  • Step 1
  • 2,4,6-trihydroxyacetophenone is initially dissolved in pyridine under an argon atmosphere and a little 4- (dimethylamino) pyridine (catalytic amount) is introduced. Now the ethyl chloroformyl formate is slowly added dropwise. After everything has been metered in, the apparatus is heated to 80 ° C. with an oil bath and stirred at this temperature for 2 hours. The apparatus is allowed to cool to room temperature, the dark brown suspension is added to about 200 ml of ice water and 200 ml of CH 2 Cl 2 are added and the mixture is extracted. The aq. Phase shaken again twice with 50mL CH 2 CI 2 and the org.
  • Oxalicacid-2-ethoxycarbonyl-7-ethoxyoxalyloxy-4-oxo-4H-chromen-5-ylesterethyl ester from step 1 is initially dissolved in ethanol at room temperature, Na 2 CO 3 dissolved in H 2 O-VE is added dropwise. The mixture is then heated to 70 ° C. and stirred for 4 hours at this temperature. After cooling, the reaction mixture is mixed with 100 ml of ethyl acetate and made weakly acidic with 1 N HCl. The aqueous phase is separated off and extracted again. The org. Phases are combined, 3x with H 2 0-VE, 1x with sat. NaCl solution.
  • the ester is obtained by transesterification of the acid from Example 4 with 1-ethylhexyl alcohol.
  • Example 5 Preparation of 5,7-diacetoxy-3-acetyl-2-methyl-chromen-4-one
  • Example 7 Representation of ⁇ -dihydroxy ⁇ -ethylpentylchromen ⁇ - one
  • 2,4,6-trihydroxyacetophenone (5g-26.3mmol) is added to 90ml toluene, 14g potassium carbonate is dissolved in 70ml demineralized water and 1g tetra-n-butylammonium hydrogen sulfate is added to the solution.
  • the filtrate is concentrated again and 100 ml of heptane are added to the distillation residue, a solid precipitating, which is suctioned off through a suction filter.
  • reaction mixture is cooled with an ice bath and in 50ml
  • ROESY spectra show the interaction of spatially neighboring atoms. Atoms close to one another give signals in the ROESY 2D-NMR spectrum. Here the complex was measured using ROESY in order to clarify which molecular components of the 5,7-dihydroxy-2-methylchromene-4-one the complex formation takes place.
  • the NMR data fit the interpretation that a complex has formed which consists of 5,7-dihydroxy-2-methyl-chromen-4-one and two cyclodextrin molecules.
  • Solubility of the 5,7-dihydroxy-2-methyl-chromen-4-one cyclodextrin complex 0.5 g of the complex is dissolved in 1 ml of water without reaching saturation. This corresponds to a solubility based on pure 5,7-dihydroxy-2-methyl-chromen-4-one of at least 34.5 mg / ml.
  • cyclodextrin complexes of the chromone derivatives are prepared according to Examples 1-5 and 7-9.
  • the name of the chromone derivative stands for the corresponding hydroxypropyl-gamma-cyclodextrin complex, the amounts given relating to the chromone derivative.
  • Preparation Phase A is heated to 75 ° C and phase B to 80 ° C.
  • Phase B is slowly added to phase A with stirring. After homogenization, the mixture is cooled with stirring.
  • Perfumes are added at a temperature of 40 ° C.
  • Phase A is heated to 75 ° C and phase B to 80 ° C.
  • Phase B is slowly added to phase A with stirring. After homogenization, the mixture is cooled with stirring. Perfumes are added at a temperature of 40 ° C.
  • Phase A is heated to 75 ° C and phase B to 80 ° C.
  • Phase B is slowly added to phase A with stirring. After homogenization, the mixture is cooled with stirring. Perfumes are added at a temperature of 40 ° C.
  • a cream (O / W) containing ectoin is produced from the following components:
  • a paraffin, low viscosity (1) 8.0 isopropyl myristate (1) 4.0 Mirasil CM5 (2) 3.0 Stearic acid (1) 3.0 Arlacel 165 V (3) 5.0 5,7-dihydroxy-2-methyl-chromen-4-one 1, 0
  • phases A and B are heated separately to 75 ° C. Then phase A is slowly added to phase B with stirring and stirred until a homogeneous mixture is formed. After homogenization of the emulsion, the mixture is cooled to 30 ° C. with stirring. The mixture is then heated to 35 ° C., phase C is added and the mixture is stirred until homogeneous.
  • Topical composition as W / O emulsion wt.%
  • a Isolan PDI 3.0 Paraffin oil, fl. (1) 17.0 isopropyl myristate 5.0 beeswax 0.2 Cutina HR (2) 0.3 5,7-dihydroxy-2-methyl-chromen-4-one 1, 0
  • Phases A and B are heated to 75 ° C. Phase B is added to phase A with stirring. The mixture is then homogenized with the Turrax at 9000 rpm for 2 min. The mixture obtained is cooled to 30 to 35 ° C. and C is stirred in.
  • UV-Pearl, OMC stands for the preparation with the INCI name: Water (for EU: Aqua), ethylhexyl methoxycinnamate, silica, PVP, chlorphenesin, BHT; this preparation is commercially available under the name Eusolex®UV Pearl TM OMC from Merck KGaA, Darmstadt.
  • UV pearls listed in the tables are each composed analogously, with OMC being replaced by the specified UV filters.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Gerontology & Geriatric Medicine (AREA)
  • Cosmetics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

L'invention concerne des complexes de certains dérivés de chromone, des préparations contenant ces dérivés, des procédés appropriés pour la production des dérivés de chromone ou des préparations les contenant, ainsi que leur utilisation, notamment pour les soins de la peau ou des cheveux et la conservation ou l'amélioration de l'état général de la peau ou des cheveux.
PCT/EP2005/002369 2004-04-02 2005-03-07 Complexes de chromone WO2005097772A1 (fr)

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US10/594,752 US20070191305A1 (en) 2004-04-02 2005-03-07 Chromone complexes
EP05715783A EP1732913A1 (fr) 2004-04-02 2005-03-07 Complexes de chromone

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DE102004016250A DE102004016250A1 (de) 2004-04-02 2004-04-02 Chromon-Komplexe
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* Cited by examiner, † Cited by third party
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WO2007087956A1 (fr) * 2006-01-31 2007-08-09 Merck Patent Gmbh Dérivés de chromène-4-one comme substance autobronzante

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DE102011009112A1 (de) * 2011-01-21 2012-07-26 Merck Patent Gmbh Chromen-4-on-Derivate
CN104230868B (zh) * 2014-05-21 2016-04-27 广东鑫钰新材料股份有限公司 化合物2-甲基-5,7-二羟基色酮的一种化学制备方法

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WO2007087956A1 (fr) * 2006-01-31 2007-08-09 Merck Patent Gmbh Dérivés de chromène-4-one comme substance autobronzante

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